US3006883A - Method of producing a phenol formaldehyde acetone resin - Google Patents
Method of producing a phenol formaldehyde acetone resin Download PDFInfo
- Publication number
- US3006883A US3006883A US769320A US76932058A US3006883A US 3006883 A US3006883 A US 3006883A US 769320 A US769320 A US 769320A US 76932058 A US76932058 A US 76932058A US 3006883 A US3006883 A US 3006883A
- Authority
- US
- United States
- Prior art keywords
- acetone
- formaldehyde
- resin
- producing
- phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920005989 resin Polymers 0.000 title claims description 17
- 239000011347 resin Substances 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 6
- OQYNBATYDVDEMV-UHFFFAOYSA-N formaldehyde;phenol;propan-2-one Chemical compound O=C.CC(C)=O.OC1=CC=CC=C1 OQYNBATYDVDEMV-UHFFFAOYSA-N 0.000 title description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000009102 absorption Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- YIBPLYRWHCQZEB-UHFFFAOYSA-N formaldehyde;propan-2-one Chemical compound O=C.CC(C)=O YIBPLYRWHCQZEB-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 methylol derivatives of acetone Chemical class 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/26—Condensation polymers of aldehydes or ketones with phenols only from mixtures of aldehydes and ketones
Definitions
- thermosetting resin having high flexibility, good bonding strength, and good water absorp tion.
- n moles of acetone will also react with 11 moles and also with 3n moles of formaldehyde, leading to resin formation.
- These polymers have poor mechanical properties and poor heat resistance.
- Example I The following materials were used in preparing a laminating resin:
- the acetone is introduced into a reaction vessel fitted with an agitator and a reflux condenser.
- the acetone is brought to reflux and 1020 gm. of formaldehyde (12.60 moles) and 2.66 gm. of sodium carbonate (0.025 mole) are gradually added separately such that 10 equal portions of each are added at 10 minute intervals,
- the resin is then distilled under high vacuum to a temperature of C. After the water has been removed, 618 gm. of methanol are added, giving a clear, viscous laminating varnish suitable for the production of high quality thermosetting paper or cloth laminates.
- This varnish was used for impregnating 60 lb. kraft paper (basis 3,000 sq. ft.) to a resin content of 33% and a volatile content of 7.9%, and the resultant material laminated by pressing for forty-five minutes at C. under 800 p.s.i. with the following results.
- Heat resistance Can be drawn hot from the press (160 C.) without blisters. Shows no surface injury and no blistering when subjected to A.S.T.M. (D1300-53T) high-temperature test.
- Cigarette-burn test 201 seconds (A.S.T.M., 111300-531).
- thermosetting laminating resin comprisingreacting acetone and formaldehyde in alkaline solution to form a monomeric monomethylol derivative thereof, and reacting said derivative with phenol and *thereafter with additional formaldehyde to f-fonn'the thermosetting resin.
- A'method accordingto claim 1 wherein approx- 4 imately 1.0 mole of acetone and 1.0-1.5 moles of formaldehyde are reacted in' alkaline solution to form the monomeric monomethylol derivative.
Description
United States Patent 3,006,883 METHOD OF PRODUCING A PHENOL FORMALDEHYDE ACETONE RESIN Emile A. Cambron, Cornwall, Ontario, Canada, assignor to Howard Smith Paper Mills Limited, Montreal, Quebec, Canada No Drawing. Filed Oct. 24, 1958, Ser. No. 769,320
3 Claims. (Cl. 260-43) The purpose of this invention is to prepare a new and valuable thermosetting resin.
It is a further object of this invention to prepare a resin having good flexibility while retaining good bonding, good flexural strength, and good resistance to water absorption and being suitable for the production of thermosetting laminates.
I have discovered that acetone, together with phenol and formaldehyde, can, under rigidly controlled conditions, lead to a valuable thermosetting resin having high flexibility, good bonding strength, and good water absorp tion.
It is known to the art that acetone will react with formaldehyde to form methylol derivatives of acetone which will further undergo polymerization leading to thermoplastic low molecular weight polymers.
An example of acetone formaldehyde polymerization is as follows:
In addition to 11 moles of acetone reacting with 2n moles of formaldehyde, n moles of acetone will also react with 11 moles and also with 3n moles of formaldehyde, leading to resin formation. These polymers have poor mechanical properties and poor heat resistance.
It has been suggested that phenol or a phenolic resin be added to these polymers to attain better heat stability. However, results obtained with these resins, although to some extent heat hardenable, are not truly thermosetting. Thus, if such a resin is used in paper or cloth based laminates, the resulting products when drawn hot from the press, blister and delaminate as a result of the rapid escape of water vapor from the still soft material. These resins have not been found to be commercially acceptable.
I have found that phenol or cresol or mixtures thereof can be introduced into the reaction, to form a copolymer at the stage where the methylol derivatives of acetone are substantially in the monomeric form.
Due to the greater reactivity of the alpha-hydrogen of the phenol molecule over the alpha-hydrogen of the acetone molecule, the formation of acetone-formaldehyde polymers may be minimized by adding the phenol with the acetone.
However, due again to the difference in reactivity of their respective alpha-hydrogen atoms the earlier the acetone is introduced in the reaction the higher the yield. I have found that the best yields of a satisfactory resin are obtained by initiating the reaction between acetone and formaldehyde to yield a substantially monomeric product under mildly alkaline conditions and then introducing phenol equimolecularly proportioned to the acetone, before the substantially monomeric product has 3,006,883 Patented Oct. 31, 1961 ice polymerized into the undesired inferior quality acetone formaldehyde resin.
Example I The following materials were used in preparing a laminating resin:
The acetone is introduced into a reaction vessel fitted with an agitator and a reflux condenser. The acetone is brought to reflux and 1020 gm. of formaldehyde (12.60 moles) and 2.66 gm. of sodium carbonate (0.025 mole) are gradually added separately such that 10 equal portions of each are added at 10 minute intervals,
After an additional 10 minutes reflux following the 10th addition of formaldehyde 665 gm. phenol, 166 gm. cresol and 2.66 gm. (0.025 mole) of sodium carbonate are added and the resultant solution is refluxed for 30 minutes.
This is followed by 1020 gm. of formaldehyde 12.60 moles) and 6.10 gm. of sodium carbonate (0.057 mole) which are gradually added separately such that 5 equal portions of each are added at 10 minute intervals. Further formaldehyde, 1020 gm. (12.60 moles) and catalyst, 7.59 gm. of sodium carbonate (0.072 mole), are then added and reflux carried for a period of 60 minutes. An additional 7.59 gm. of sodium carbonate (0.072 mole) is added and the resultant solution is refluxed for 20 minutes.
The resin is then distilled under high vacuum to a temperature of C. After the water has been removed, 618 gm. of methanol are added, giving a clear, viscous laminating varnish suitable for the production of high quality thermosetting paper or cloth laminates.
This varnish was used for impregnating 60 lb. kraft paper (basis 3,000 sq. ft.) to a resin content of 33% and a volatile content of 7.9%, and the resultant material laminated by pressing for forty-five minutes at C. under 800 p.s.i. with the following results.
Water absorption of predried sample during 24 hours immersion in distilled water (A.S.T.M.).
D570-54T), percent:
Heat resistance: Can be drawn hot from the press (160 C.) without blisters. Shows no surface injury and no blistering when subjected to A.S.T.M. (D1300-53T) high-temperature test.
Used in a decorative laminate with printed melamine impregnated surface sheet shows no surface injury and no blistering when subjected to A.S.T.M. (D1300- 53T) high-temperature test.
Cigarette-burn test: 201 seconds (A.S.T.M., 111300-531).
What I claim is:
1. A method of producing a thermosetting laminating resincomprisingreacting acetone and formaldehyde in alkaline solution to form a monomeric monomethylol derivative thereof, and reacting said derivative with phenol and *thereafter with additional formaldehyde to f-fonn'the thermosetting resin.
'2. A'method accordingto claim 1 wherein approx- 4 imately 1.0 mole of acetone and 1.0-1.5 moles of formaldehyde are reacted in' alkaline solution to form the monomeric monomethylol derivative.
3. A method according to claim 2 wherein phenol in approximate equimolecular proportion With the acetone is reacted with said delivative.
References Cited in the file of this'patent UNITED STATES PATENTS 10 2,191,802 Novotny et a1. "Feb. 27, 1940 2,206,906 'LOOS July 9, 1940 2,538,884 Schrimpe Jan. 23, 1951
Claims (1)
1. A METHOD OF PRODUCING A THERMOSETTING LAMINATING RESIN COMPRISING REACTION ACETONE AND FORMALDEHYDE IN ALKALINE SOLUTION TO FORM A MONOMERIC MONOMETHYLOL DERIVATIVE THEREOF, AND REACTING SAID DERIVATE WITH PHENOL AND THEREAFTER WITH ADDITIONAL FORMALDEHYDE TO FORM THE THERMOSETTING RESIN.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US769320A US3006883A (en) | 1958-10-24 | 1958-10-24 | Method of producing a phenol formaldehyde acetone resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US769320A US3006883A (en) | 1958-10-24 | 1958-10-24 | Method of producing a phenol formaldehyde acetone resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3006883A true US3006883A (en) | 1961-10-31 |
Family
ID=25085108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US769320A Expired - Lifetime US3006883A (en) | 1958-10-24 | 1958-10-24 | Method of producing a phenol formaldehyde acetone resin |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3006883A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3321358A (en) * | 1965-12-20 | 1967-05-23 | Mobil Oil Corp | Plywood bonded with a resinous composition comprising a ketone-aldehyde resin and a chemically basic clay |
| US3390127A (en) * | 1964-03-24 | 1968-06-25 | Mobil Oil Corp | Water-soluble ketone-aldehyde-phenol resins and process of making same |
| US3410813A (en) * | 1966-03-30 | 1968-11-12 | Mobil Oil Corp | Composition board made from material pretreated with a fluxed water repellent |
| US3533880A (en) * | 1967-09-29 | 1970-10-13 | Dow Chemical Co | Method for adhering polymethyl methacrylate to a substrate |
| US4011280A (en) * | 1973-12-21 | 1977-03-08 | Deutsche Texaco Aktiengesellschaft | Process for the production of binders for weather-proof wood materials and product |
| US4169937A (en) * | 1975-12-19 | 1979-10-02 | Societa' Italiana Resine S.I.R. S.P.A. | Method for preparing a granular thermosetting moulding composition containing a novolak having modified surface characteristics |
| US20090018304A1 (en) * | 2005-01-25 | 2009-01-15 | Hodogaya Chemical Co., Ltd. | Ketone-modified resorcinol-formalin resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2191802A (en) * | 1937-12-27 | 1940-02-27 | Emil E Novotny | Preparation of fusible ketonealdehyde synthetic resins |
| US2206906A (en) * | 1937-02-27 | 1940-07-09 | Loos Karl | Resinous condensates and method of producing same |
| US2538884A (en) * | 1947-07-18 | 1951-01-23 | Union Carbide & Carbon Corp | Acetone-formaldehyde resins |
-
1958
- 1958-10-24 US US769320A patent/US3006883A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2206906A (en) * | 1937-02-27 | 1940-07-09 | Loos Karl | Resinous condensates and method of producing same |
| US2191802A (en) * | 1937-12-27 | 1940-02-27 | Emil E Novotny | Preparation of fusible ketonealdehyde synthetic resins |
| US2538884A (en) * | 1947-07-18 | 1951-01-23 | Union Carbide & Carbon Corp | Acetone-formaldehyde resins |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3390127A (en) * | 1964-03-24 | 1968-06-25 | Mobil Oil Corp | Water-soluble ketone-aldehyde-phenol resins and process of making same |
| US3321358A (en) * | 1965-12-20 | 1967-05-23 | Mobil Oil Corp | Plywood bonded with a resinous composition comprising a ketone-aldehyde resin and a chemically basic clay |
| US3410813A (en) * | 1966-03-30 | 1968-11-12 | Mobil Oil Corp | Composition board made from material pretreated with a fluxed water repellent |
| US3533880A (en) * | 1967-09-29 | 1970-10-13 | Dow Chemical Co | Method for adhering polymethyl methacrylate to a substrate |
| US4011280A (en) * | 1973-12-21 | 1977-03-08 | Deutsche Texaco Aktiengesellschaft | Process for the production of binders for weather-proof wood materials and product |
| US4169937A (en) * | 1975-12-19 | 1979-10-02 | Societa' Italiana Resine S.I.R. S.P.A. | Method for preparing a granular thermosetting moulding composition containing a novolak having modified surface characteristics |
| US20090018304A1 (en) * | 2005-01-25 | 2009-01-15 | Hodogaya Chemical Co., Ltd. | Ketone-modified resorcinol-formalin resin |
| US7834124B2 (en) * | 2005-01-25 | 2010-11-16 | Hodogaya Chemical Co., Ltd. | Ketone-modified resorcinol-formalin resin |
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